Azo dyes having a benzoisothiazolyl diazo component

Abstract

P-aminoazo dyes of the formula: ##STR1## in which D is a benzoisothiazolyl group;

B¹ is hydrogen, methyl, ethyl, methoxy, ethoxy;

B² is hydrogen, methyl, ethyl, methoxy, ethoxy, chloro, bromo, C₁ to C₄ alkanoylamino or C₁ to C₄ alkoxycarbonylamino;

R¹ is the radical ##STR2## C₁ to C₄ alkyl optionally bearing hydroxy, C₁ to C₄ alkoxy, C₁ to C₄ alkanoyloxy, C₁ to C₄ alkoxycarbonyl, C₁ to C₄ alkanoylamino or chloro as a substituent, phenylethyl, phenoxyethyl or cyclohexyl and the group -A¹ --CO--A² represents acyl, acyloxy or acylamino derived from a carbonic acid derivative in which A¹ is a single bond, --O--, --NH-- or ##STR3##

Description

The invention relates to dyes of the formula (I): ##STR4## in which D is a radical of the formula: ##STR5## X is nitro, chloro or bromo; Y is hydrogen, chloro or bromo;

Z is hydrogen, chloro, bromo or cyano;

B¹ is hydrogen, methyl, ethyl, methoxy, ethoxy or phenoxy;

B² is hydrogen, methyl, ethyl, methoxy, ethoxy, chloro, bromo, C₁ to C₄ alkanoylamino or C₁ to C₄ alkoxycarbonylamino;

R¹ is C₁ to C₄ alkyl optionally bearing hydroxy, C₁ to C₄ alkoxy, C₁ to C₄ alkanoyloxy, C₁ to C₄ alkoxycarbonyl, C₁ to C₄ alkanoylamino or chloro as a substituent, cyclohexyl, phenylethyl, phenoxyethyl or a radical of the formula: ##STR6## A¹ is a direct bond, --O--, --NH-- or ##STR7## A² is a radical of the formula ##STR8##

or (when A¹ is --NH-- or --O--) may also be --O--A⁵ ;

A³ is hydrogen, C₁ to C₈ alkyl optionally bearing hydroxy, C₁ to C₄ alkoxy, chloro, cyano, C₁ to C₄ alkoxycarbonyl, C₁ to C₄ alkanoylamino, C₁ to C₄ alkylaminocarbonyloxy, C₁ to C₄ alkoxycarbonyloxy or C₁ to C₄ alkanoyloxy as a substituent, allyl, cyclohexyl, benzyl, or phenyl optionally bearing chloro, bromo, methyl or C₁ to C₄ alkoxycarbonyl as a substituent;

A⁴ is hydrogen or C₁ to C₄ alkyl optionally bearing hydroxy, chloro, C₁ to C₄ alkoxy or C₁ to C₄ alkanoyloxy as a substituent;

A⁵ is C₁ to C₄ alkyl optionally bearing hydroxy, chloro, C₁ to C₄ alkoxy, C₁ to C₄ alkanoyloxy or C₁ to C₄ alkylaminocarbonyloxy as a substituent, cyclohexyl or phenyl; and

Q is a radical of the formula ##STR9##

Examples of alkanoylamino radicals B² are: butyrylamino, propionylamino, formylamino and particularly acetylamino and also NHCOOCH₃, NHCOOC₂ H₅, NHCOOC₃ H₇ and NHCOOC₄ H₉.

Examples of radicals R¹ other than those already specified are: C₂ H₄ OC₃ H₇, C₂ H₄ OC₄ H₉, C₂ H₄ OCOC₄ H₉, C₂ H₄ OCOC₃ H₇, C₂ H₄ OCOC₂ H₅, ##STR10## C₂ H₄ COOC₄ H₉, C₃ H₆ NHCOCH₃, C₂ H₄ COOC₃ H₇, C₂ H₄ Cl, particularly CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₂ H₄ OH, C₂ H₄ CN, CH₂ CHOHCH₃, C₂ H₄ OCH₃, C₂ H₄ OC₂ H₅, C₂ H₄ OCOCH₃, C₂ H₄ COOCH₃ and C₂ H₄ COOC₂ H₅.

Examples of radicals Q--A¹ --CO--A² are: C₂ H₄ CONHCH₃, C₂ H₄ CON(CH₃)₂, C₂ H₄ CONHC₂ H₅, C₂ H₄ CON(C₂ H₅)₂, ##STR11## C₂ H₄ CONHC₃ H₇, C₂ H₄ CONHC₄ H₉, C₂ H₄ CON(C₄ H₉)₂, ##STR12## C₂ H₄ CONHC₂ H₄ CN, ##STR13## C₂ H₄ CONHC₂ H₄ OCH₃, C₂ H₄ CONHC₃ H₆ OCH₃, C₂ H₄ CONHC₂ H₄ OC₂ H₅, C₂ H₄ CONHC₂ H₄ OC₂ H₄ OH, C₂ H₄ CONHC₂ H₄ OH, ##STR14## C₂ H₄ CON(C₂ H₄ OH)₂, C₂ H₄ CONHC₃ H₆ OH, C₂ H₄ CONHCH₂ CHOHCH₃, C₂ H₄ CONHC₂ H₄ OCOCH₃, C₂ H₄ CONHC₂ H₄ OCOC₃ H₇, ##STR15## C₂ H₄ CONHC₃ H₆ OCOCH₃, C₂ H₄ CONHC₂ H₄ OCONHCH₃, C₂ H₄ CONHC₂ H₄ OCONHC₄ H₉, C₂ H₄ CONHC₂ H₄ OCOOCH₃, C₂ H₄ CONHC₂ H₄ NHCOCH₃, C₂ H₄ CONHC₂ H₄ NHCOC₃ H₇, C₂ H₄ OCONH₂, C₂ H₄ OCONHCH₃, ##STR16## C₂ H₄ OCON(CH₃)₂, C₂ H₄ OCONHC₂ H₅, C₂ H₄ OCON(C₂ H₅)₂, C₂ H₄ OCONHCH₂ -CH═CH₂, C₂ H₄ OCONHC₃ H₇, C₂ H₄ OCONHC₄ H₉, C₂ H₄ OCON(C₄ H₉)₂, C₂ H₄ OCONHC₅ H₁1, C₂ H₄ OCONH(CH₂)₅ CN, C₂ H₄ OCONHC₆ H₁3, C₂ H₄ OCONHC₇ H₁5, C₂ H₄ OCONHC₈ H₁7, ##STR17## C₂ H₄ OCONHCH₂ COOCH₃, C₂ H₄ OCONHCH₂ COOC₂ H₅, C₂ H₄ OCONH(CH₂)₂ COOCH₃, C₂ H₄ OCONH(CH₂)₃ COOCH₃, C₂ H₄ OCONHC₂ H₄ Cl, C₂ H₄ OCONHC₂ H₄ OCOCH₃, C₂ H₄ OCONHC₂ H₄ OH, C₂ H₄ OCONHC₃ H₆ OH, C₂ H₄ OCONHC₂ H₄ CN, C₂ H₄ OCON(C₂ H₄ CN)₂, ##STR18## C₂ H₄ OCOOC₂ H₄ OCH₃, C₂ H₄ OCOOC₃ H₆ OCH₃, C₂ H₄ OCOOC₂ H₄ OC₂ H₅, CH₂ CH₂ OCH₂ CH₂ OCOOCH₃, C₂ H₄ OCOOC₂ H₄ Cl, ##STR19## C₃ H₆ NHCON(CH₃)₂, C₃ H₆ NHCONHC₂ H₅, C₃ H₆ NHCON(C₂ H₅)₂, C₃ H₆ NHCONHC₃ H₇, C₃ H₆ NHCONHC₄ H₉, C₂ H₄ NHCONHC₄ H₉, C₃ H₆ NHCONHC₆ H₁3, ##STR20## C₃ H₆ NHCONHCH₂ COOCH₃, C₃ H₆ NHCONHCH₂ COOCH₂ H₅, C₃ H₆ NHCONH(CH₂)₂ COOCH₃, C₃ H₆ NHCONHC₂ H₄ CN, ##STR21## C₃ H₆ NHCOOC₂ H₄ OCH₃, C₃ H₆ NHCOOC₂ H₄ OC₂ H₅, C₃ H₆ NHCOOC₃ H₆ OCH₃, C₃ H₆ NHCOOC₂ H₄ Cl, C₂ H₄ NHCOOC₂ H₄ OH, C₃ H₆ NHCOOC₂ H₄ OH, C₃ H₆ NHCOOC₃ H₆ OH, C₃ H₆ NHCOOC₂ H₄ OCOCH₃, C₃ H₆ NHCOOC₂ H₄ OCONHCH₃, ##STR22##

Dyes of the formula (Ia): ##STR23## in which D¹ is 5-nitrobenzoisothiazolyl-(2,1), 5-nitro-7-bromobenzoisothiazolyl-(2,1), 7-nitrobenzoisothiazolyl-(1,2), 5-bromo-7-nitrobenzoisothiazolyl-(1,2) or 5-cyano-7-nitrobenzoisothiazolyl-(1,2);

B³ is hydrogen, methoxy or ethoxy;

B⁴ is hydrogen, chloro, methyl, acetylamino or propionylamino; and

R² is C₁ to C₄ alkyl, C₁ to C₄ alkoxyethyl, C₁ to C₄ alkoxypropyl, β-cyanoethyl, β-chloroethyl, β-hydroxyethyl, β-hydroxypropyl, β-C₁ to C₄ alkanoyloxyethyl, β-C₁ to C₄ alkanoyloxypropyl, C₁ to C₄ alkoxycarbonyl, phenylethyl or a radical of the formula ##STR24## in which A¹ and A² have the above meanings are of particular technical importance.

Examples of preferred radicals ##STR25## are: C₂ H₄ CONHCH₃, C₂ H₄ CONHC₂ H₅, C₂ H₄ CONHC₃ H₇, C₂ H₄ CONHC₄ H₉, C₂ H₄ CONHC₂ H₄ OCH₃, C₂ H₄ CONHC₃ H₆ OCH₃, C₂ H₄ CONHC₂ H₄ OH, ##STR26## C₂ H₄ CONHC₃ H₆ OH, C₂ H₄ CONHCH₂ CHOHCH₃, C₂ H₄ CONHC₂ H₄ OCOCH₃, C₂ H₄ NHC₂ H₄ OCOC₃ H₇, ##STR27## C₂ H₄ CONHC₃ H₆ OCOCH₃, C₂ H₄ CONHC₂ H₄ OCONHCH₃, C₂ H₄ CONHC₂ H₄ OCONHC₄ H₉, C₂ H₄ OCONHCH₃, ##STR28## C₂ H₄ OCON(CH₃)₂, C₂ H₄ OCON(C₂ H₅)₂, C₂ H₄ OCONHC₃ H₇, C₂ H₄ OCONHC₄ H₉, C₂ H₄ OCONHCH₂ COOC₂ H₅, C₂ H₄ OCONHCH₂ COOCH₃, C₂ H₄ OCONHC₂ H₄ Cl, ##STR29## C₂ H₄ OCOOC₂ H₅, C₂ H₄ OCOOC₃ H₇, C₂ H₄ OCOOC₄ H₉, ##STR30## C_2H4 OCOOC₂ H₄ OCH₃, C₂ H₄ OCOOC₃ H₆ OCH₃, C₂ H₄ OCOOC₂ H₄ Cl; C₃ H₆ NHCONHCH₃, C₃ H₆ NHCON(CH₃)₂, C₃ H₆ NHCON(C₂ H₅)₂, C₃ H₆ NHCONHC₃ H₇, C₃ H₆ NHCONHC₄ H₉, C₃ H₆ NHCONHCH₂ COOC₂ H₅, ##STR31## C₃ H₆ NHCOOCH₃, C₃ H₆ NHCOOC₂ H₅, C₃ H₆ NHCOOC₃ H₇, C₃ H₆ NHCOOC₄ H₉, ##STR32## C₂ H₄ OCOOC₂ H₄ OCH₃, C₂ H₄ OCOOC₃ H₆ OCH₃, C₂ H₄ OCOOC₂ H₄ OC₂ H₅, C₃ H₆ NHCOOC₂ H₄ Cl and C₃ H₆ NHCOOC₂ H₄ OH.

Particularly preferred meanings are:

D¹ : 5-nitrobenzoisothiazolyl-(2,1), 7-nitrobenzoisothiazolyl-(1,2), 5-bromo-7-nitrobenzoisothiazolyl-(1,2) or 5-cyano-7-nitrobenzoisothiazolyl-(1,2);

B³ : hydrogen;

B⁴ : hydrogen, methyl or acetylamino; and

R² : methyl, ethyl, methoxyethyl, β-cyanoethyl, β-hydroxyethyl, or a radical of the formula ##STR33##

Particularly preferred radicals ##STR34## are:

C₂ H₄ CONHC₂ H₄ OH, ##STR35## C₂ H₄ CONHC₃ H₆ OH, C₂ H₄ CONHCH₂ CHOHCH₃, C₂ H₄ CONHC₂ H₄ OCOCH₃, ##STR36## C₂ H₄ CONHC₃ H₆ OCOCH₃, C₂ H₄ OCONHCH₃, C₂ H₄ OCON(CH₃)₂, C₂ H₄ OCONHC₄ H₉, C₃ H₆ NHCONHCH₃, C₃ H₆ NHCONHC₄ H₉, C₃ H₆ NHCOOCH₃ and C₃ H₆ NHCOOC₂ H₄ OH.

Dyes of the formula (I) may be prepared by reacting a diazonium compound of an amine of the formula (II):

d--nh₂ (ii)

with a coupling component of the formula (III): ##STR37## where D, B¹, B², R¹, A¹ and A² have the above meanings, the diazotization and coupling being carried out as usual.

Dyes of the formula (I) are red to greenish blue and are suitable for dyeing synthetic and cellulosic fibers and particularly cellulose esters and polyesters.

Dyeings are obtained which show deep shades and generally have very good wet and light fastness properties and also resistance to high temperatures. In the case of dyes suitable for cellulose esters the very good fastness to gas fume fading, dry cleaning and perspiration may be stressed and in the case of the polyester dyes fastness to thermofixation and fastness properties after thermofixation.

The following Examples illustrate the invention. In them the references to parts and percentages are by weight unless otherwise stated.

EXAMPLE 1

19.5 parts of 3-amino-5-nitro-2,1-benzoisothiazole is introduced into 100 parts of 85% sulfuric acid at from 10° to 15°C 30 parts of nitrosylsulfuric acid (with a content of 13.1% of dinitrogen trioxide) is dripped into this solution at 0° to 5°C The diazo solution obtained is stirred for another three hours at 0° to 5°C and then dripped into a solution of 25 parts of N-ethyl-N-β-[N'-methyl-N'-(β-hydroxyethyl)]-carbamoyl-ethylanili ne, 40 parts of 10% hydrochloric acid, 500 parts of water, 500 parts of ice and 1 part of sulfamic acid. The whole is then neutralized to pH 1.5 with sodium acetate solution, and the precipitated dye is suction filtered, washed with water until neutral and dried at subatmospheric pressure at 50°C 31 parts of the dye of the formula: ##STR38## is obtained; it gives on polyesters and preferentially on cellulose esters intense blue dyeings with good fastness properties and particularly good fastness to light, wet treatment and dry cleaning.

EXAMPLE 2

9.7 Parts of 4-amino-7-nitro-1,2-benzoisothiazole is introduced at 10° to 15°C into 100 parts of 85% sulfuric acid. 15 parts of nitrosylsulfuric acid (with a content of 13.1% of dinitrogen trioxide) is dripped into this solution at from 0° to 5°C The diazo solution obtained is stirred for another three hours at 0° to 5°C and then dripped into a solution of 13.9 parts of N-ethyl-N-β-(N'-β-acetoxyethyl)-carbamoylethyl-aniline, 20 parts of 10% hydrochloric acid, 250 parts of water, 250 parts of ice and 1 part of sulfamic acid. Neutralization to pH 1.5 is then carried out with sodium acetate solution, the precipitated dye is suction filtered, washed with water until neutral and dried at subatmospheric pressure at 50°C 31 parts of the dye of the formula: ##STR39## is obtained which gives intense violet dyeings having good fastness properties on polyesters and cellulose esters.

EXAMPLE 3

19.5 Parts of 3-amino-5-nitro-2,1-benzoisothiazole is introduced at from 10° to 15°C into 100 parts of 85% sulfuric acid. 30 parts of nitrosylsulfuric acid (having a content of 13.1% of dinitrogen trioxide) is dripped into this solution at 0° to 5°C The diazo solution obtained is stirred for another three hours at from 0° to 5°C and then dripped into a solution of 22.2 parts of N-ethyl-N-[β-(methylaminocarbonyloxy)-ethyl]-aniline, 40 parts of 10% hydrochloric acid, 500 parts of water, 500 parts of ice and 1 part of sulfamic acid. The whole is then neutralized to pH 1 with sodium acetate solution. The precipitated dye is suction filtered, washed with water until it is neutral and dried at subatmospheric pressure at 50°C 32 parts of the dye of the formula: ##STR40## is obtained. It gives intense blue dyeings with good fastness properties on polyesters and cellulose esters.

EXAMPLE 4

19.5 Parts of 3-amino-5-nitro-2,1-benzoisothiazole is introduced at from 10° to 15°C into 100 parts of 85% sulfuric acid. 30 parts of nitrosylsulfuric acid (13.1% of N₂ O₃) is dripped into this solution at from 0° to 5°C The diazo solution obtained is stirred for 3 hours at from 0° to 5°C and then dripped into a solution of 26.4 parts of N-ethyl-N-[β-(n-butylaminocarbonyloxy)-ethyl]-aniline, 40 parts of 10% hydrochloric acid, 500 parts of water, 500 parts of ice and 1 part of sulfamic acid. The whole is then neutralized to pH 1.5 with sodium acetate. The precipitated dye is suction filtered, washed with water until it is neutral and dried at 50°C at subatmospheric pressure. 33 parts of the dye of the formula ##STR41## is obtained which gives intense blue dyeings with good fastness properties on polyesters.

EXAMPLE 5

13.7 Parts of 4-amino-5-bromo-7-nitro-1,2-benzoisothiazole is dissolved in 100 parts of 96% sulfuric acid at from 10° to 15°C Then 30 parts of a mixture (17:3) of glacial acetic acid and propionic acid is gradually added to the solution at from 0° to 5°C and diazotization is effected by dripping in 15 parts of nitrosylsulfuric acid (13.1% of N₂ O₃) at 0° to 5°C The whole is stirred for another three hours at 0° to 5°C and the diazo solution is run into a solution of 13.2 parts of N-ethyl-N-[β-(n-butylcarbamoyloxy)ethyl]-aniline, 20 parts of 10% hydrochloric acid, 250 parts of water, 200 parts of ice and 1 part of sulfamic acid. The pH is adjusted to 1.5 with sodium acetate solution, and the precipitated dye is suction filtered, washed with water until it is neutral and dried at subatmospheric pressure at 50°C 22 parts of the dye of the formula: ##STR42## is obtained. It gives an intense reddish blue having good fastness properties on polyesters.

EXAMPLE 6

5.5 Parts of 4-amino-5-cyano-7-nitrobenzoisothiazole-(1,2) is introduced at 10°C into a mixture of acids consisting of 50 parts of 85% sulfuric acid and 15 parts of a mixture (17:3) of glacial acetic acid and propionic acid. 9.5 parts of nitrosylsulfuric acid (11.1% N₂ O₃) is added at from 0° to 5°C and the mixture is stirred for four hours at this temperature. Excess nitrosylsulfuric acid is destroyed in the usual way. The diazo solution is added in portions to a solution, cooled to from 0° to 5°C, of 9.6 parts of N-ethyl-N-[-β-(n-butylamino-carbonyloxy)-ethoxy]-m-toluidine in 100 parts by volume of glacial acetic acid and at the same time 250 parts of ice is introduced gradually. After the coupling is completed the dye is suction filtered, washed with water until it is neutral and dried at 50°C at subatmospheric pressure.

10.4 parts of the dye of the formula: ##STR43## is obtained. It gives very intense dyeings having outstanding fastness properties on polyesters.

EXAMPLE 7

19.5 Parts of 3-amino-5-nitro-2,1-benzoisothiazole is introduced at from 10° to 15°C into 100 parts of 85% sulfuric acid. 30 parts of nitrosylsulfuric acid (having a content of 13.1% of dinitrogen trioxide) is dripped in at from 0° to 5°C The diazo solution obtained is stirred at from 0° to 5°C for three hours and then dripped into a solution of 26.6 parts of N-ethyl-N-(carbo-β-oxyethoxyaminopropyl)-aniline, 40 parts of 10% hydrochloric acid, 500 parts of water, 500 parts of ice and 1 part of sulfamic acid. Then the pH is adjusted to 1 with sodium acetate solution. The precipitated dye is suction filtered, washed with water until it is neutral and dried at 50°C at subatmospheric pressure. 33 parts of the dye of the formula: ##STR44## is obtained. It gives intense blue dyeings having good fastness properties on polyesters and cellulose esters.

EXAMPLE 8

9.7 Parts of 4-amino-7-nitrobenzoisothiazole-(1,2) is introduced into 100 parts of 85% sulfuric acid at from 10° to 15°C 15 parts of nitrosylsulfuric acid (with a content of 13.1% of dinitrogen trioxide) is dripped into this solution at from 0° to 5°C The diazo solution obtained is stirred for another 3 hours at 0° to 5° C. and then dripped into a solution of 14.0 parts of N-ethyl-N-(carbo-β-oxyethoxy-aminopropyl)-m-toluidine, 40 parts of 10% hydrochloric acid, 500 parts of water, 500 parts of ice and 1 part of sulfamic acid. The pH is then adjusted to 1 with sodium acetate solution. The precipitated dye is suction filtered, washed with water until it is neutral and dried at 50°C at subatmospheric pressure. 34 parts of the dye of the formula: ##STR45## is obtained. It gives intense violet dyeings on polyesters and cellulose esters.

EXAMPLE 9

5.5 Parts of 4-amino-5-cyano-7-nitrobenzoisothiazole-(1,2) is introduced at 10°C into a mixture of acids consisting of 50 parts of 85% sulfuric acid and 15 parts by volume of a mixture (17:3) of glacial acetic acid and propionic acid. 9.5 parts of nitrosylsulfuric acid (11.1% of N₂ O₃) is added at from 0° to 5°C and the mixture is stirred for four hours at this temperature. The excess of nitrosylsulfuric acid is destroyed as usual. The diazo solution is added in portions to a solution, cooled to 0° to 5°C, of 5.5 parts of N-ethyl-N-[γ-(methoxycarbonylamino)-propyl-]aniline in 100 parts by volume of glacial acetic acid and 250 parts of ice is gradually added at the same time. When the coupling has been completed the dye is suction filtered, washed with water until it is neutral and dried at 50°C at subatmospheric pressure. 8.7 parts of the dye of the formula: ##STR46## is obtained. It dyes polyesters full blue hues having good fastness properties.

EXAMPLE 10

5.5 parts of 4-amino-5-cyano-7-nitrobenzoisothiazole is introduced at 10°C into a mixture of acids consisting of 50 parts 85% sulfuric acid and 15 parts by volume of a mixture (17:3) of glacial acetic acid and propionic acid. 9.5 parts of nitrosylsulfuric acid (M = 342) is added thereto at from 0° to 5°C and the mixture is stirred for 4 hours at this temperature. The excess of nitrosylsulfuric acid is destroyed in the usual way. The diazo solution is added in portions to a solution, cooled to 0° to 5°C, of 6.9 parts of N-ethyl-N-[γ-(n-butylaminocarbonylamino)-propyl]-aniline in 100 parts by volume of glacial acetic acid and at the same time 250 parts of ice is gradually introduced. After the coupling is ended the dye is suction filtered, washed with water to make it neutral and dried at 50 °C at subatmospheric pressure. 9.8 parts of the dye of the formula: ##STR47## is obtained. It gives intense blue dyeings having good fastness properties on polyesters.

Dyes of the formula (I) which are hereinafter characterized by specifying their substituents are also obtained by methods analogous to those described in Examples 1 to 10.

TBL3 No. DK B¹ B² R¹ alkylene A¹ A² Hue 11 ##STR48## H H C₂ H₄ OH C₂ H₄ -- NHCH₃ blue 12 " H H C₂ H₅ C₂ H₄ -- NHC₂ H₄ OH " 13 " H H CH₂ CHOHCH₂ Cl C₂ H₄ -- NHC₂ H₄ OH " 14 " H H C₂ H₅ C₂ H₄ -- NHC₃ H₆ OH " 15 " H H C₂ H₅ C₂ 44 -- NHC₂ H₄ OC₂ H₄ OH " 16 " H H C₂ H₅ C₂ H₄ -- NHCH₂ CHOHCH₃ " 17 " H H C₂ H₅ C₂ H₄ -- ##STR49## " 18 " H H C₂ H₅ C₂ H₄ -- NHC₂ H₄ OCOCH₃ " 19 " H H C₂ H₅ C₂ H₄ -- NHC₂ H₄ NHCOCH₃ " 20 " H CH₃ C₂ H₅ C₂ H₄ O NHCH₃ " 21 " H CH₃ CH₃ C₂ H₄ O NHCH₃ " 22 " H H C₂ H₄ OCH₃C₂ H₄ O NHCH₃ " 23 " H NHCOCH₃ C₂ H₄ OCONHCH₃ C₂ H₄ O NHCH₃ greenish blue 24 " H H C₂ H₄ COOCH₃ C₂ H₄ O NHCH₃ blue 25 " H CH₃ C₂ H₄ OCONHCH₃ C₂ H₄ O NHCH₃ " 26 " H H C₂ H₅ ##STR50## O NHCH₃ " 27 " H H C₂ H₅ ##STR51## O NHCH₃ " 28 " H H C₂ H₅ C₂ H₄ O N(CH₃)₂ " 29 " H H C₂ H₅ C₂ H₄ O NHCH₂ COOC₂ H₅ " 30 " H H C₂ H₄ OCOCH₃ C₂ H₄ O NHC₂ H₄ Cl " 31 " H H C₂ H₅ C₂ H₄ O NHC₂ H₄ OH " 32 " H H C₂ H₅ C₂ H₄ O ##STR52## " 33 " H CH₃ C₂ H₅ C₂ H₄ O NHC₄ H₉ " 34 " H CH₃ CH₃ C₂ H₄ O NHC₄ H₉ " 35 " OCH₃ NHCOCH₃ C₂ H₄ CN C₂ H₄ O NHC₄ H₉ greenish blue 36 " H CH₃ C₂ H₅ C₂ H₄ O NH(CH₂)₅ CN blue 37 " H H C₂ H₄ CN C₂ H₄ O OCH₃ bluish violet 38 " H H C₂ H₄ OCOOCH₃ C₂ H₄ O OCH₃ " 39 " H H C₂ H₄ OC₂ H₅ C₂ H₄ O OC₂ H₄ Cl " 40 " H H C₂ H₅ C₂ H₄ O OC₄ H₉ " 41 " H H C₂ H₅ C₃ H₆ NH NHCH₃ blue 42 " H H C₂ H₅ C₃ H₆ NC₂ H₄ CN NHC₄ H₉ " 43 " H H C₂ H₅ C₃ H₆ NH N(CH₃)₂ " 44 " H H C₂ H₅ C₃ H₆ NH ##STR53## " 45 " H H C₂ H₅ C₃ H₆ NH OCH₃ " 46 " H H CH₃ C₃ H₆ NH OCH₃ " 47 " H CH₃ C₂ H₅ C₃ H₆ NH OC₂ H₄ OH " 48 " H H C₂ H₅ C₂ H₄ NH OC₂ H₄ OH " 49 " H H C₂ H₅ C₃ H₆ NH OC₂ H₄ OCOCH₃ " 50 " H H C₂ H₅ C₃ H₆ NH ##STR54## " 51 ##STR55## H H C₂ H₅ C₂ H₄ -- NHC₂ H₄ OCOCH₃ greenish blue 52 " H H C₄ H₉ C₂ H₄ -- NHC₂ H₄ OCONHCH₃ " 53 " H H C₂ H₅ C₂ H₄ -- NHC₂ H₄ OCH₃ " 54 " H H C₂ H₅ ##STR56## O NHCH₃ " 55 " H H C₂ H₅ C₂ H₄ O NHC₄ H₉ " 56 " H H C₂ H₅ C₂ H₄ O NH(C₄ H₉)₂ " 57 " H H C₂ H₅ C₂ H₄ O NHCH₂ COOC₂ H₅ " 58 " H H C₂ H₅ C₂ H₄ O NHCH₂CHCH₂ " 59 " H H C₂ H₅ C₂ H₄ O ##STR57## " 60 " H H C₂ H₅ C₂ H₄ O OCH₃ " 61 " H H ##STR58## C₂ H₄ O OCH₃ " 62 " H H C₂ H₅ C₃ H₆ NH NHC₄ H₉ " 63 " H H C₂ H₅ C₃ H₆ NH ##STR59## " 64 " H H C₂ H₅ C₃ H₆ NH NHCH₃ " 65 " H H C₂ H₅ C₃ H₆ NH OC₂ H₄ OH " 66 " H CH₃ CH₃ C₃ H₆ NH OC₂ H₄ OH " 67 " H H C₂ H₅ C₃ H₆ NH OC₂ H₄ OCONHC₄ H₉ " 68 " H CH₃ C₂ H₅ C₃ H₆ NH ##STR60## " 69 ##STR61## H H C₂ H₅ C₂ H₄ -- ##STR62## " 70 " H CH₃ C₂ H₅ C₂ H₄ O NHC₄ H₉ " 71 " H H C₂ H₅ C₃ H₆ NH OC₂ H₄ OH " 72 ##STR63## H H C₂ H₄ OH C₂ H₄ -- NHC₂ H₄ NHCOC₃ H₇ violet 73 " H H C₂ H₅ C₂ H₄ O NHC₄ H₉ " 74 " H H C₂ H₅ ##STR64## O ##STR65## " 75 ##STR66## H H C₂ H₄ Cl C₂ H₄ -- NHC₃ H₇ (n) " 76 " H H C₂ H₅ C₂ H₄ O NHC₃ H₇ (i) " 77 " H H C₂ H₅ C₂ H₄ O ##STR67## " 78 " H H C₂ H₅ C₃ H₆ NH NHC₂ H₄ Cl" 79 ##STR68## H H C₂ H₄ OCOC₃ H₇ C₂ H₄ -- NHC₄ H₉ " 80 " H H C₂ H₅ C₂ H₄ -- NHC₂ H₄ OH " 81 " H H C₂ H₅ C₂ H₄ -- NHC₃ H₆ OCOCH₃ " 82 " H H C₂ H₅ CH₂ -- ##STR69## " 83 " H H C₂ H₅ C₂ H₄ -- NHC₂ H₄ OCOC₃ H₇ " 84 " H H C₂ H₅ ##STR70## O NHCH₃ " 85 " H HNCOCH₃ C₂ H₄ OCONHCH₃ C₂ H₄ O NHCH₃ bluish violet 86 " H H C₂ H₄ COOC₄ H₉ C₂ H₄ O NHCH₃ violet 87 " H H C₂ H₄ CN C₂ H₄ O NHCH₃ reddish violet 88 " H Cl C₂ H₄ OCONHCH₃ C₂ H₄ O NHCH₃ " 89 " OC₂ H₅ NHCOCH₃ C₂ H₄ OCONHCH₃ C₂ H₄ O NHCH₃ bluish violet 90 " H H C₂ H₅ C₂ H₄ O N(CH₃)₂ violet91 " H H ##STR71## C₂ H₄ O ##STR72## " 92 " H H C₂ H₅ C₂ H₄ O OC₄ H₉ " 93 " H NHCOCH₃ C₂ H₄ OCOOC₂ H₅ C₂ H₄ O OC₂ H₅ bluish violet 94 " H H C₂ H₅ C₂ H₄ O ##STR73## violet 95 " H CH₃ C₂ H₅ C₃ H₆ NH NHCH₃ " 96 " H CH₃ C₃ H₆ NHCOCH₃ C₃ H₆ NH NHCH₃ " 97 " H H C₂ H₅ C₃ H₆ NH N(C₄ H₉)₂ " 98 " H H C₂ H₅ C₃ H₆ NH OCH₃ " 99 " H H C₂ H₅ C₃ H₆ NH OC₂ H₄ OH" 100 " H H C₂ H₅ C₃ H₆ NH OC₂ H₄ OCONHCH₃ " 101 ##STR74## H H C₃ H₇ C₂ H₄ -- NHC₂ H₄ OCOCH₃ bluish violet 102 " H H C₂ H₅ C₂ H₄ O NH₂ " 103 " H NHCOCH₃ C₂ H₄ OCONHC₄ H₉ C₂ H₄ O NHC₄ H₉ blue 104 " H C₂ H₅ CH₃ C₂ H₄ O ##STR75## bluish violet 105 " H H C₂ H₅ ##STR76## O OCH₃ " 106 " H H C₂ H₅ C₃ H₆ NH NHC₄ H₉ " 107 " H H C₄ H₉ C₃ H₆ NH ##STR77## " 108 ##STR78## H H C₂ H₄ OCOC₃ H₇ C₂ H₄ -- N(CH₃)₂ " 109 " H H ##STR79## C₂ H 4 -- NHC₂ H₅ " 110 " H H C₂ H₅ C₂ H₄ -- NHC₃ H₆ OCOCH₃ " 111 " H H C₂ H₅ C₂ H₄ -- NHC₂ H₄ OCOC₃ H₇ " 112 " H H C₂ H₄ OCONHCH₃ C₂ H₄ -- NHC₂ H₄ OCONHCH₃ " 113 " H H C₂ H₅ C₂ H₄ -- NHC₂ H₄ OCOOCH₃ " 114 " H CH₃ C₂ H₅ C₂ H₄ O NHCH₃ " 115 ##STR80## H H ##STR81## ##STR82## O NHCH₃ " 116 " CH₃ H C₂ H₄ OCONHCH₃ C₂ H₄ O NHCH₃ " 117 " H H C₂ H₅ ##STR83## O NHCH₃ " 118 " H NHCHO C₂ H₄ OCONHC₄ H₉ C₂ H₄ O NHC₄ H₉ blue 119 " H H C₂ H₅ C₂ H₄ O NHC₆ H₁3 bluish violet 120 " H H C₂ H₅ ##STR84## O OCH₃ " 121 " ##STR85## NHCOCH₃ C₂ H₄ CN C₂ H₄ OOCH₃ blue 122 " H H CH₂ CHOHCH₃ ##STR86## O OC₂ H₄ Cl bluish violet 123 " H CH₃ C₂ H₅ C₂ H₄ O OC₂ H₄ OCH₃ " 124 " H CH₃ C₂ H₅ C₃ H₆ NH NHC₄ H₉ blue 125 " H H C₂ H₅ C₃ H₆ NC₂ H₄ CN NHCH₃ " 126 " H CH₃ C₃ H₆ NHCONHCH₃ C₃ H₆ NH NHCH₃ " 127 " H H C₂ H₄ OCH₃ C₃ H₆ NH ##STR87## " 128 " H CH₃ C₂ H₅ C₃ H₆ NH OC₂ H₄ OH " 129 " H H C₂ H₅ C₃ H₆ NH OC₂ H₄ OCOCH₃ " 130 " H CH₃ C₂ H₅ C₃ H₆ NH OC₄ H₉ " 131 " H CH₃ C₂ H₅ C₃ H₆ NH OC₂ H₄ Cl " 132 " H CH₃ C₂ H₅ C₃ H₆ NH OCH₃ " 133 ##STR88## H H C₂ H₄ OCONHCH₃ C₂ H₄ -- NHC₂ H₅ " 134 " H CH₃ C₂ H₅ C₂ H₄ -- NHC₂ H₄ OCOCH₃ " 135 " H CH₃ C₂ H₅ C₂ H₄ -- NHC₂ H₄ OCOC₃ H₇ " 136 " H CH₃ C₂ H₅ C₂ H₄ -- NHC₂ H₄ NHCOC₃ H₇ " 137 " H CH₃ C₂ H₅ C₂ H₄ -- ##STR89## " 138 " H CH₃C₂ H₅ C₂ H₄ O NHCH₃ " 139 " H NHCOC₃ H₇ C₂ H₄ OCONHCH₃ C₂ H₄ O NHCH₃ greenish blue 140 " H H C₂ H₅ ##STR90## O NHCH₃ blue 141 " C₂ H₅ H C₂ H₄ OH C₂ H₄ O NHCH₃ " 142 " H CH₃ C₂ H₅ ##STR91## O NHCH₃ " 143 " H CH₃ C₂ H₅ C₂ H₄ O NHC₃ H₇ (i) " 144 " H CH₃ C₂ H₅ C₂ H₄ O NHC₂ H₄ CN " 145 " H CH₃ C₂ H₅ C₂ H₄ O N(C₂ H₄ Cl)₂ " 146 " H CH₃ CH₂ CHOHCH₃ ##STR92## O NHC₄ H₉ " 147 " H H C₃ H₇ C₂ H₄ O NHC₄ H₉ " 148 " H CH₃ ##STR93## C₂ H₄ ONHC₄ H₉ " 149 " H H C₂ H₅ C₂ H₄ O ##STR94## " 150 " H CH₃ C₂ H 5 C₂ H₄ O OCH₃ " 151 " H H ##STR95## C₂ H₄ O OC₃ H₇ " 152 " H CH₃ C₂ H₅ C₂ H₄ O OC₃ H₆ OCH₃ " 153 " H CH₃ C₂ H₅ C₃ H₆ NH NHCH₃ greenish blue 154 " H CH₃ C₂ H₅ C₃ H₆ NH NHC₄ H₉ " 155 " H H C₂ H₅ C₂ H₄ NH NHC₄ H₉ blue 156 " H CH₃ C₂ H₅ C₃ H₆ NH ##STR96## greenish blue 157 " H CH₃ C₂ H₅ C₃ H₆ NH NHC₆ H₁3 " 158 " H CH₃ C₂ H₅ C₃ H₆ NH OCH₃ " 159 " H CH₃ C₂ H₅ C₃ H₆ NH OC₂ H₅ " 160 " H CH₃ C₂ H₅ C₃ H₆ NH ##STR97## " 161 " H CH₃ C₂ H₅ C₃ H₆ NH OC₂ H₄ OH " 162 " H CH₃ C₂ H₅ C₃ H₆ NH OC₂ H₄ OCH₃ " 163 ##STR98## H H C₂ H₅ C₂ H₄ O NHC₂ H₅ blue 164 " H H C₂ H₄ CN C₂ H₄ O NHC₄ H₉ " 165 " H CH₃ C₂ H₅ C₂ H₄ -- ##STR99## " 166 " H CH₃ C₂ H₅ C₂ H₄ -- NHC₂ H₄ OH "

Claims

1. A dye having the formula ##STR100## in which: D¹ is 5-nitrobenzoisothiazolyl-(2,1), or

5-cyano-7-nitrobenzoisothiazolyl-(1,2);

B⁴ is hydrogen or methyl;

R² is C₁ to C₄ alkyl, C₁ to C₄ alkoxyethyl, β-cyanoethyl or β-hydroxyethyl;

A¹ is a direct bond, --NH-- or --O--;

A² is NH--(C₁ to C₄)-alkyl, NH--C₂ H₄ OH, NH--C₃ H₆ OH, or ##STR101## or, when A¹ is --NH-- or --O--, is OCH₃, OC₂ H₅ or OC₂ H₄ OH; and

Q is --C₂ H₄ --, --C₃ H₆ -- or --C₄ H₈ --.

2. The dye having the formula: ##STR102##

3. The dye having the formula: ##STR103##

4. The dye having the formula: ##STR104##

5. The dye having the formula: ##STR105##

6. The dye having the formula: ##STR106##

7. The dye having the formula: ##STR107##

8. The dye having the formula: ##STR108##